Carbohydrate polyamine binders and materials made therewith

ABSTRACT

A binder comprising the products of a carbohydrate reactant and polyamine is disclosed. The binder is useful for consolidating loosely assembled matter, such as fibers. Uncured fibrous products comprising fibers in contact with a carbohydrate reactant and a polyamine are also disclosed. The binder composition may be cured to yield a fibrous product comprising fibers bound by a cross-linked polymer. Further disclosed are methods for binding fibers with the carbohydrate reactant and polyamine based binder.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/867,526, filed May 5, 2020, which is a continuation of U.S.application Ser. No. 15/911,411 (now U.S. Pat. No. 10,738,160), filedMar. 5, 2018, which is a continuation of U.S. application Ser. No.15/332,257 (now abandoned), filed Oct. 24, 2016, which is a continuationof U.S. application Ser. No. 14/272,556 (now U.S. Pat. No. 9,505,883),filed May 8, 2014, which is a continuation of U.S. application Ser. No.13/696,439 (now abandoned), filed Nov. 6, 2012, which is a nationalstage entry under 35 U.S.C. § 371(b) of International Application No.PCT/EP2011/057363, filed May 7, 2011, which claims the benefit under 35U.S.C. § 119(e) of U.S. provisional application 61/332,458, filed May 7,2010, the disclosures of each of which are incorporated by referenceherein in their entirety.

TECHNICAL FIELD

This disclosure relates to a binder formulation and materials madetherewith comprising a carbohydrate-based binder and a method forpreparing the same. In particular, a binder comprising the reactionproducts of a carbohydrate reactant and a polyamine and materials madetherewith is described.

BACKGROUND

Binders are useful in fabricating articles because they are capable ofconsolidating non- or loosely-assembled matter. For example, bindersenable two or more surfaces to become united. In particular, binders maybe used to produce products comprising consolidated fibers.Thermosetting binders may be characterized by being transformed intoinsoluble and infusible materials by means of either heat or catalyticaction. Examples of a thermosetting binder include a variety ofphenol-aldehyde, urea-aldehyde, melamine-aldehyde, and othercondensation-polymerization materials like furane and polyurethaneresins. Binder compositions containing phenol-aldehyde,resorcinol-aldehyde, phenol/aldehyde/urea, phenol/melamine/aldehyde, andthe like are used for the bonding of fibers, textiles, plastics,rubbers, and many other materials.

The mineral wool and fiber board industries have historically used aphenol formaldehyde binder to bind fibers. Phenol formaldehyde typebinders provide suitable properties to the final products; however,environmental considerations have motivated the development ofalternative binders. One such alternative binder is a carbohydrate basedbinder derived from reacting a carbohydrate and a multiprotic acid, forexample, U.S. Published Application No. 2007/0027283 and Published PCTApplication WO2009/019235. Another alternative binder is theesterification products of reacting a polycarboxylic acid and a polyol,for example, U.S. Published Application No. 2005/0202224. Because thesebinders do not utilize formaldehyde as a reagent, they have beencollectively referred to as formaldehyde-free binders.

One area of current development is to find a replacement for the phenolformaldehyde type binders across the entire range of products in thebuilding and automotive sector (e.g. fiberglass insulation, particleboards, office panels, and acoustical sound insulation). In particular,the previously developed formaldehyde-free binders may not possess allof the desired properties for all the products in this sector. Forexample, acrylic acid and poly(vinylalcohol) based binders have shownpromising performance characteristics. However, these are relativelymore expensive than phenol formaldehyde binders, are derived essentiallyfrom petroleum-based resources, and have a tendency to exhibit lowerreaction rates compared to the phenol formaldehyde based bindercompositions (requiring either prolonged cure times or increased curetemperatures). Carbohydrate-based binder compositions are made ofrelatively inexpensive precursors and are derived mainly from renewableresources; however, these binders may also require reaction conditionsfor curing that are substantially different from those conditions underwhich the traditional phenol formaldehyde binder system cured. As such,facile replacement of phenol formaldehyde type binders with an existingalternative has not been readily achievable.

SUMMARY

According to the present disclosure, a carbohydrate based binder isdescribed. The binder composition has properties that make it useful fora variety of applications; particularly, the binder may be used to bindloosely assembled matter such as fibers.

In illustrative embodiments, the present disclosure relates to a bindercomprising a polymeric product of a carbohydrate reactant and apolyamine. In one embodiment, the carbohydrate reactant is apolysaccharide. In one embodiment, the carbohydrate reactant is amonosaccharide or a disaccharide. In another embodiment, thecarbohydrate is a monosaccharide in its aldose or ketose form. Inanother embodiment, the carbohydrate reactant is selected from a groupconsisting of dextrose, xylose, fructose, dihydroxyacetone, and mixturesthereof. In another embodiment, the polymeric product is a thermosetpolymeric product.

In illustrative embodiments, the polyamine is a primary polyamine. Inone embodiment, the polyamine may be a molecule having the formula ofH₂N-Q-NH₂, wherein Q is an alkyl, cycloalkyl, heteroalkyl, orcycloheteroalkyl, each of which may be optionally substituted. In oneembodiment, Q is an alkyl selected from a group consisting of C₂-C₂₄. Inanother embodiment, Q is an alkyl selected from a group consisting ofC₂-C₈. In another embodiment, Q is an alkyl selected from a groupconsisting of C₃-C₇. In yet another embodiment, Q is a C₆ alkyl. In oneembodiment, Q is selected from the group consisting of a cyclohexyl,cyclopentyl or cyclobutyl. In another embodiment, Q is a benzyl.

In illustrative embodiments, the polyamine is selected from a groupconsisting of a diamine, triamine, tetraamine, and pentamine. In oneembodiment, the polyamine is a diamine selected from a group consistingof 1,6-diaminohexane and 1,5-diamino-2-methylpentane. In one embodiment,the diamine is 1,6-diaminohexane. In one embodiment, the polyamine is atriamine selected from a group consisting of diethylenetriamine,1-piperazineethaneamine, and bis(hexamethylene)triamine. In anotherembodiment, the polyamine is a tetramine such as triethylenetetramine.In another embodiment, the polyamine is a pentamine, such astetraethylenepentamine.

In illustrative embodiments, the primary polyamine is apolyether-polyamine. In one embodiment, the polyether-polyamine is adiamine or a triamine.

In illustrative embodiments, the weight ratio of the carbohydratereactant to the polyamine is in the range of about 1:1 to about 30:1. Inanother embodiment, the weight ratio of the carbohydrate reactant to thepolyamine is in the range of about 2:1 to about 10:1. In anotherembodiment, an aqueous extract of the polymeric product has a pH in therange of about 5 to about 9. In another embodiment, an aqueous extractof the polymeric product is essentially colorless. In yet anotherembodiment, the polymeric product is phenol-free and/orformaldehyde-free. In another embodiment, an aqueous extract of thepolymeric product is capable of reducing Benedict's reagent. In anotherembodiment, the polymeric product absorbs light between 400 and 500 nm,for example, at 420 nm.

In an illustrative embodiment, a method of making a collection of matterbound with a polymeric binder comprises preparing a solution containingreactants for producing the polymeric binder and a solvent, wherein thereactants include a carbohydrate reactant and a polyamine; disposing thesolution onto the collection of matter; volatilizing the solvent to forman uncured product, and subjecting the uncured product to conditionsthat cause the carbohydrate reactant and the polyamine to polymerize toform the polymeric binder. In one embodiment, the collection of mattercomprises fibers selected from a group consisting of mineral fibers(slag wool fibers, rock wool fibers, or glass fibers), aramid fibers,ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyesterfibers, rayon fibers, and cellulosic fibers. In another embodiment, thecollection of matter comprises particulates such as coal or sand. Inanother embodiment, the collection of matter is glass fibers. In yetanother embodiment, the glass fibers are present in the range from about70% to about 99% by weight. In another embodiment, the collection ofmatter comprises cellulosic fibers. For example, the cellulosic fibersmay be wood shavings, sawdust, wood pulp, or ground wood. In yet anotherembodiment, the cellulosic fibers may be other natural fibers such asjute, flax, hemp, and straw.

In illustrative embodiments, the method of making a collection of matterbound with a polymeric binder further includes preparing a solution byadding an amount of a carbohydrate reactant and an amount of a polyamineso that the weight ratio is in the range of about 2:1 to about 10:1,respectively. In one embodiment, preparing the solution includes addingthe carbohydrate reactant and the polyamine to an aqueous solution. Inanother embodiment, preparing the solution includes adjusting the pH ofthe solution to within the range of about 8 to about 13, for example,the range of about 8 to about 12.

In illustrative embodiments, the present disclosure relates to acomposition comprising a collection of matter and a binder; the bindercomprising the polymeric products of a reaction between a carbohydratereactant and a polyamine, the polymeric products being substantiallywater insoluble. In one embodiment, the collection of matter includesmineral fibers (slag wool fibers, rock wool fibers, or glass fibers),aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimidefibers, polyester fibers, rayon fibers, and cellulosic fibers. Forexample, cellulosic fibers include wood shavings, sawdust, wood pulp,and/or ground wood. In one embodiment, the carbohydrate reactant isselected from a group consisting of dextrose, xylose, fructose,dihydroxyacetone, and mixtures thereof. In another embodiment, thepolyamine is selected from a group consisting of a diamine, triamine,tetramine, and pentamine. In one embodiment, the polyamine is H₂N-Q-NH₂,wherein Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, eachof which is optionally substituted. In another embodiment, thecomposition further comprises a silicon-containing compound. In oneembodiment the silicon-containing compound is a functionalizedsilylether or a functionalized alkylsilylether, such as for example, anamino-functionalized alkylsilylether. For example, in one embodiment,the silicon-containing compound may be gamma-aminopropyltriethoxysilane,gamma-glycidoxypropyltrimethoxysilane, oraminoethylaminopropyltrimethoxysilane, or a mixture thereof. In anotherembodiment, the silicon-containing compound may be an aminofunctionaloligomeric siloxane. In another embodiment, the composition comprises acorrosion inhibitor selected from a group consisting of dedusting oil,monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin(II)oxalate, and a methylhydrogen silicone fluid emulsion.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic of a Maillard reaction, which culminates in theproduction of melanoidins.

FIG. 2 shows a schematic of a representative Amadori rearrangement.

FIG. 3 shows the cure temperature profile (Y-axis in ° C.) of the centerof a fiberglass mat sample for different binders during a heat moldingcycle (X-axis in minutes of mold time) using a mold press with atemperature controlled platen at 204° C. Binder 1 (♦) is a phenolformaldehyde binder (Comparative Example 2); Binder 2 (▪) is acarbohydrate-inorganic acid binder (Comparative Example 3); and Binder 3(X) is a dextrose-ammonia-hexamethylene diamine (HMDA) binder (Example5).

DETAILED DESCRIPTION

While the invention is susceptible to various modifications andalternative forms, specific embodiments will herein be described indetail. It should be understood, however, that there is no intent tolimit the invention to the particular forms described, but on thecontrary, the intention is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the invention.

The present disclosure relates to a binder composition having unexpectedutility in consolidating non- or loosely-assembled matter. The bindercomposition represents an unexpected advancement in the current state oftechnology in the area of binder compositions. Specifically, the binderoffers improvements in performance and provides for more simplified andadvantageous manufacturing methodologies, while maintaining theenvironmentally sound advantages that are characteristic of acarbohydrate based binder system.

As used herein, the term binder solution is the solution of chemicalswhich can be substantially dehydrated to form an uncured binder. As usedherein, the binder or binder composition may be cured, uncured, orpartially cured. The composition of the uncured binder is referred to asan uncured binder composition. An uncured binder is a substantiallydehydrated mixture of chemicals which can be cured to form a curedbinder. Substantially dehydrated means that the solvent (typically wateror a mixture thereof) used to make the binder solution is vaporized tothe extent that the viscosity of the remaining material (comprising thebinder reactants and solvent) is sufficiently high to create cohesionbetween the loosely assembled matter; thus, the remaining material is anuncured binder. In one embodiment, the solvent is less than 65% of thetotal weight of the remaining material. In another embodiment, asubstantially dehydrated binder has a moisture content between about 5%and about 65% water by weight of total binder. In another embodiment,the solvent may be less than 50% of the total weight of the remainingmaterial. In yet another embodiment, the solvent may be less than 35% ofthe total weight of the remaining material. In another embodiment, asubstantially dehydrated binder has between about 10% and about 35%water by weight of total binder. In another embodiment, the solvent maycomprise less than about 20% of the total weight of the remainingmaterial.

In illustrative embodiments, an uncured binder may be colorless, white,off white, ochre or yellow to brownish sticky substance that is, atleast partially, water soluble. As used herein, the term cured binderdescribes the polymeric product of curing the uncured bindercomposition. The cured binder may have a characteristic brown to blackcolor. While described as brown or black, another characteristic is thatthe binder tends to absorb light over a broad range of wavelengths. Inparticular, there may be higher absorbance at approximately 420 nm. Asthe polymer is extensively cross-linked, the cured binder issubstantially insoluble. For example, the binder is predominantlyinsoluble in water. As described herein, the uncured binder providessufficient binding capacity to consolidate fibers; however, the curedbinder imparts the robust, long-lasting durability and physicalproperties commonly associated with cross-linked polymers.

In illustrative embodiments, the binder reactants described herein aresoluble in water and the binder solution is a solution of the binderreactants in an aqueous solution. In one embodiment, a surfactant isincluded in the aqueous solution to increase the solubility ordispersability of one or more binder reactants or additives. Forexample, a surfactant may be added to the aqueous binder solution toenhance the dispersibility of a particulate additive. In one embodiment,a surfactant is used to create an emulsion with a non-polar additive orbinder reactant. In another embodiment, the binder solution comprisesabout 0.01% to about 5% surfactant by weight based on the weight of thebinder solution.

In illustrative embodiments, the binder solutions described herein canbe applied to mineral fibers (e.g., sprayed onto the mat or sprayed ontothe fibers as they enter the forming region), during production ofmineral fiber insulation products. Once the binder solution is incontact with the mineral fibers the residual heat from the mineralfibers (note that glass fibers for example are made from molten glassand thus contain residual heat) and the flow of air through and/oraround the product will cause a portion of the water to evaporate fromthe binder solution. Removing the water leaves the remaining componentsof the binder on the fibers as a coating of viscous or semi-viscoushigh-solids mixture. This coating of viscous or semi-viscous high-solidsmixture functions as a binder. At this point, the mat has not beencured. In other words, the uncured binder functions to bind the mineralfibers in the mat.

Furthermore, it should be understood that the above described uncuredbinders can be cured. For example, the process of manufacturing a curedinsulation product may include a subsequent step in which heat isapplied as to cause a chemical reaction in the uncured bindercomposition. For example, in the case of making fiberglass insulationproducts or other mineral fiber insulating products, after the bindersolution has been applied to the fibers and dehydrated, the uncuredinsulation product may be transferred to a curing oven. In the curingoven the uncured insulation product is heated (e.g., from about 300° F.to about 600° F. [from about 150° C. to about 320° C.]), causing thebinder to cure. The cured binder is a formaldehyde-free, water-resistantbinder that binds the fibers of the insulation product together. Notethat the drying and thermal curing may occur either sequentially,simultaneously, contemporaneously, or concurrently.

In illustrative embodiments, an uncured fiber product comprises about 3%to about 40% of dry binder solids (total uncured solids by weight). Inone embodiment, the uncured fiber product comprises about 5% to about25% of dry binder solids. In another embodiment, the uncured fiberproduct comprises about 50% to about 97% fibers by weight.

As mentioned herein with respect to a binder on mineral fibers, a curedbinder is the product of curing binder reactants. The term curedindicates that the binder has been exposed to conditions so as toinitiate a chemical change. Examples of these chemical changes include,but are not limited to, (i) covalent bonding, (ii) hydrogen bonding ofbinder components, and (iii) chemically cross-linking the polymersand/or oligomers in the binder. These changes may increase the binder'sdurability and solvent resistance as compared to the uncured binder.Curing a binder may result in the formation of a thermoset material. Inaddition, a cured binder may result in an increase in adhesion betweenthe matter in a collection as compared to an uncured binder. Curing canbe initiated by, for example, heat, microwave radiation, and/orconditions that initiate one or more of the chemical changes mentionedabove. While not limited to a particular theory, curing may include thereaction of the carbohydrate and the polyamine to form melanoidins.

In a situation where the chemical change in the binder results in therelease of water, e.g., polymerization and cross-linking, a cure can bedetermined by the amount of water released above that which would occurfrom drying alone. The techniques used to measure the amount of waterreleased during drying as compared to when a binder is cured, are wellknown in the art.

One aspect of the present disclosure is that the cured bindercomposition comprises a nitrogenous polymer. The nitrogenous polymer isbrown to black in color. While not limited to a particular theory, thecured binder composition comprises melanoidins. Melanoidins areidentifiable as being brown, high molecular weight, complex, furanring-containing and nitrogen-containing polymers. High molecular weight,as used herein, includes those polymers having a molecular weight inexcess of 100,000 Daltons. Being comprised of highly cross-linkedpolymeric chains, the molecular weight of the melanoidins describedherein approaches infinity. Accordingly, the molecular weight of amelanoidin may be a function of the mass and physical dimensions of thepolymer being analyzed. For example, a unitary sample of melanoidinshaving a mass of 3 grams may be presumed to comprise a single polymericmolecule due to the extensive cross-linking. Accordingly, the molecularweight of the polymer would be approximately 1.8×10²⁴ grams per mole(being the product of the sample mass and Avogadro's number). As usedherein, a high molecular weight polymer includes polymers with amolecular weight in the order of between about 1×10⁵ and about 1×10²⁴grams per mole.

While not be limited to a particular theory, it is known thatmelanoidins vary in structure according to the reactants and conditionsof preparation. It is also known that melanoidins possess a carbon tonitrogen ratio which increases with temperature and time of heating.Furthermore, melanoidins possess saturated, unsaturated and aromaticcharacter. For melanoidins, the degree of unsaturation and aromaticityincreases with temperature (cure temperature) and time of heating (curetime). Melanoidins also contain the C-1 of those sugars incorporated asreactants in a variety of structures within the melanoidin. Melanoidinsmay also contain carbonyl, carboxyl, amine, amide, pyrrole, indole,azomethine, ester, anhydride, ether, methyl and/or hydroxyl groups.Depending on the complexity of the structure, infrared spectroscopy maybe useful in the identification of one or more of these functionalgroups. While described as a melanoidin-type polymer herein, one ofordinary skill would appreciate that the binder may also be classifiableaccording to the existence of a particular bond present such as apolyester, polyether, polyamide, etc.

Another manner in which the binder is characterizable is throughanalysis of the gaseous compounds produced during pyrolysis of the curedbinder. Gas pyrolysis of a cured binder within the scope of the presentdisclosure may yield approximately 0.5 to about 15% (by relative peakarea) of one or more of the following compounds: 2-cyclopenten-1-one,2,5-dimethyl-furan, furan, 3-methyl-2,5-furandione, phenol,2,3-dimethyl-2-cyclopenten-1-one, 2-methyl phenol, 4-methyl phenol,2,4-dimethyl-phenol, dimethylphthalate, octadecanoic acid, orerucylamide. Fingerprinting in pyrolysis gas chromatography massspectrometry (Py GC-MS) carried out at 770° C. of a binder sampleprepared using hexamethylenediamine as the polyamine component showspyridine and a number of components which are pyrrole or pyridinederivatives (a methyl pyridine, a methyl pyrrole, dimethyl pyridines, adimethyl pyrrole, an ethyl methyl pyrrole, and other pyrrole relatedN-containing components). Another manner in which the binder may beidentified is whether a solution containing the binder (or an extractsolution) is capable of reducing Benedict's reagent. In one embodiment,a solution in contact with the binder or an aqueous extract thereofreduces Benedict's reagent.

One aspect of the present disclosure is that the binders describedherein are environmentally friendly. Parallel to advancing governmentregulation, the present disclosure describes a binder that may be madeformaldehyde-free. Additionally, the chemistry described herein isessentially free of formaldehyde and phenol. In this sense, neitherformaldehyde nor phenol is used as a reagent within the scope of thepresent disclosure. While both may be added to obtain a binder withpotentially useful properties, one aspect of the present disclosure is abinder that can be made free from both of these reactants. In anotheraspect, the present binder composition may be manufactured without theuse of volatile reactants. In one embodiment, the primary amine and thecarbohydrate are both non-volatile reactants. As used herein, a volatilereactant is one that has a vapor pressure greater than 10 kPa at 20° C.Similarly, as used herein, a non-volatile reactant has a vapor pressureof less than about 10 kPa at 20° C. Specifically and as an example, thepresent binder may be manufactured without the addition of ammonia or anammonia releasing compound. In one embodiment, the polyamine has a vaporpressure of less than about 0.5 kPa at 60° C.

Another environmentally friendly aspect of the present disclosure isthat the primary reactants of the binder are carbohydrates.Carbohydrates are considered a renewable resource. However, the currentstate of the art primarily uses petroleum-derived reactants for themanufacture of binder compositions. In another aspect, the binder ismade through chemical reactions which can occur at lower temperaturesthan those comparable systems described in the prior art. As such, thecuring ovens and manufacturing equipment can be operated at lowertemperatures, saving valuable resources. In the alternative and in arelated manner, the binder described herein cures more quickly thancomparable binders currently used when subjected to similar curingtemperatures. Accordingly, through either approach, one aspect of thepresent disclosure is that the carbon footprint of a formed productusing the presently disclosed binder may be substantially reducedcompared to a comparable binder made according to the current state ofthe art, for example a phenol formaldehyde based product.

In addition to the environmental benefits, the present bindercomposition and materials made therewith can be made having performancecharacteristics equivalent or exceeding those of comparable bindersystems, for example phenol formaldehyde binders. In one aspect, abinder according to the present disclosure provides articles madetherewith sufficient tensile strength to allow for die-cutting,fabrication, lamination, and installation in OEM applications. In oneaspect, a binder according to the present disclosure has water hold-up(weatherability) comparable to that of a phenol formaldehyde binder.Other performance characteristic that may be relevant for a particularapplication include product emissions, density, loss on ignition,thickness recovery, dust, tensile strength, parting strength, durabilityof parting strength, bond strength, water absorption, hot surfaceperformance, corrosivity on steel, flexural rigidity,stiffness-rigidity, compressive resistance, conditioned compressiveresistance, compressive modulus, conditioned compressive modulus, andsmoke development on ignition. One aspect of the present disclosure isthat the extract of the cured binder is essentially pH neutral, forexample between a pH of 6 and 8. Another aspect of the presentdisclosure is that the present binder enables the manufacture ofproducts having comparable relevant performance characteristics tophenol formaldehyde binder compositions.

Illustratively, in one embodiment, a binder according to the presentdisclosure invention has the advantage of yielding essentially colorlessaqueous extracts. This feature of the present disclosure makes thebinder desirable in applications such as ceiling tiles, furniture, oroffice panels, wherein the finished product may come into contact withwater. A cured manufactured good made with the present binder shows anexcellent resistance to discoloration or bleeding after coming incontact with moisture or water. Furthermore, in such an embodiment, thewater that contacts the binder does not leave a residual color on otherarticles or parts which it may contact subsequent to contact the binder.For example, in one embodiment, the binder may be used to bind glassfibers in an office panel application. Covering the bound fiberglasscomposition may be a light colored fabric. Advantageously, in oneembodiment, water contacting the fiberglass composition does not leave acolored residue upon the fabric after the office panel has dried.

In addition to the performance characteristics, the manufacturingprocesses and methods involving the presently disclosed binder have anumber of unexpected advantages over previously described binders. Inone aspect, as previously described with respect to the environmentalbenefits, the present binder may be manufactured without the use ofhighly volatile reactants. Accordingly, manufacturing emission controlsare under a reduced burden. Furthermore, the reaction efficiency ishigher because reactant loss due to vaporization is reduced.Accordingly, one aspect of the present disclosure is that the compoundsused herein are substantially non-volatile, thus the steps one must taketo mitigate undesirable emissions are reduced.

According to another aspect, the reactants that react to form a binderare sufficiently slow to react such that a one step/one pot bindersystem can be used. According to this aspect, the reactant compounds aresufficiently slow to react that they can be added to a single reactantsolution and stored for a reasonable amount of time during which theycan be applied to a product using one distribution system. Thiscontrasts with those binder systems which react at low temperaturesresulting in insoluble reaction products within binder solution deliverysystems. As used here, a reasonable amount of time for storage withoutsubstantial (>5%) polymeric precipitation is two weeks.

Another aspect of the present disclosure is that, although the binder issufficiently unreactive at room temperature conditions to facilitate aone-pot approach, it is sufficiently reactive at elevated temperaturesto cure at very low temperatures and/or very short curing residencytimes. In one respect, the lowered curing temperature reduces the riskof an insulation product undergoing flameless combustion and/or causingline fires. As used here, very low temperatures are characterized asless than or equal to about 120° C. As used here, very short cure timesare less than or equal to about 4 min.

In illustrative embodiments, the binder composition includes an acid oran acid salt to increase the shelf life of the uncured binder or bindersolution. While this acid is not a reactant or a catalyst, it may beincluded to slow or inhibit the binder reactants from forming the binderwhile the binder solution or uncured binder is being maintained understorage conditions. For example, a volatile acid or acid salt may beincluded in the binder solution or uncured binder that slows or inhibitsthe curing reaction at ambient conditions. However, the acid may beremoved by heating the binder solution or uncured binder so that theacid is volatilized and the pH of the binder solution or uncured binderincreases. In one embodiment, the binder composition includes ashelf-life extending acid. In another embodiment, the binder compositionincludes a mole ratio of shelf-life extending acid to polyamine of about1:20 to about 1:1.

Another aspect of the present disclosure is a binder having a cure rate,cycle time, and cure temperature which meets or exceeds those cure ratesthat a comparable phenol and formaldehyde type binder may exhibit withinthe scope of a comparable use. In this respect, the present binder canbe used as a direct replacement to phenol formaldehyde resins inapplications without modification to the equipment. Furthermore, thepresent binder enables the modification of the curing temperature andtimes so that both the reaction temperatures and cure times may bereduced. This reduction has the effect of reducing the energyconsumption of the process overall and reduces the environmental impactof manufacturing the product. Furthermore, the lower cure temperatureshave the further effect of increasing the safety of manufacturingprocess. Another effect of the lower cure temperatures is a reduction inthe risk of flameless combustion or fire.

In the manufacture of insulation products, the heat released by theexothermic curing reaction may result in self-heating of the product.Self-heating is typically not problematic so long as the heat dissipatesfrom the product. However, if the heat increases the temperature of theproduct to the point where oxidative processes commence, theself-heating may cause significant damage to the product. For example,flameless combustion or oxidation may occur when the temperature of theinsulation product exceeds about 425° F. (210° C.). At thesetemperatures, the exothermic combustion or oxidation processes promotefurther self-heating and the binder may be destroyed. Furthermore, thetemperature may increase to a level in which fusing or devitrificationof the glass fibers is possible. Not only does this damage the structureand value of the insulation product, it may also create a fire hazard.

Another aspect of the present disclosure is that the binder system isessentially non-corrosive with or without the addition of corrosioninhibitors. Furthermore, the binder system does not require the additionof any organic or inorganic acid or salts thereof as catalyst or activeingredient. Accordingly, one aspect of the present binder is that it maybe made essentially acid-free. Furthermore, the binder may bemanufactured under entirely alkaline conditions. As used here, the termacid includes those compounds which are characterizable primarily fortheir acidic character such multiprotic inorganic and organic acids(e.g. sulfuric acid and citric acid). This aspect reduces the wear andmaintenance requirements of the manufacturing equipment and enhancesworker safety.

In illustrative embodiments, a binder comprises a polymeric product of acarbohydrate reactant and a polyamine. As used herein, the termcarbohydrate reactant refers to a monosaccharide, a disaccharide, apolysaccharide, or a reaction product thereof. In one embodiment, thecarbohydrate reactant may be a reducing sugar. As used herein, reducingsugar indicates one or more sugars that contain aldehyde groups, or thatcan isomerize, i.e., tautomerize, to contain aldehyde groups, whichgroups may be oxidized with, for example, Cu⁺² to afford carboxylicacids. It is also appreciated that any such carbohydrate reactant may beoptionally substituted, such as with hydroxy, halo, alkyl, alkoxy, andthe like. It is further appreciated that in any such carbohydratereactant, one or more chiral centers are present, and that both possibleoptical isomers at each chiral center are contemplated to be included inthe invention described herein. Further, it is also to be understoodthat various mixtures, including racemic mixtures, or otherdiastereomeric mixtures of the various optical isomers of any suchcarbohydrate reactant, as well as various geometric isomers thereof, maybe used in one or more embodiments described herein. While non-reducingsugars, for instance sucrose, may not be preferable, they maynone-the-less be useful within the scope of the present disclosure byin-situ conversion to a reducing sugar (i.e. conversion of sucrose toinvert sugar is a method known in the art). Further, it is alsounderstood that a monosaccharide, a disaccharide, or polysaccharide maybe partially reacted with a precursor to form a carbohydrate reactionproduct. To the extent that the carbohydrate reaction product is derivedfrom a monosaccharide, a disaccharide, or a polysaccharide and maintainssimilar reactivity with the polyamine to form reaction products similarto those of a monosaccharide, a disaccharide, or a polysaccharide with apolyamine, the carbohydrate reaction product is within the scope of termcarbohydrate reactant.

In one aspect, any carbohydrate reactant should be sufficientlynonvolatile to maximize its ability to remain available for reactionwith the polyamine. The carbohydrate reactant may be a monosaccharide inits aldose or ketose form, including a triose, a tetrose, a pentose, ahexose, or a heptose; or a polysaccharide; or combinations thereof. Forexample, when a triose serves as the carbohydrate reactant, or is usedin combination with other reducing sugars and/or a polysaccharide, analdotriose sugar or a ketotriose sugar may be utilized, such asglyceraldehyde and dihydroxyacetone, respectively. When a tetrose servesas the carbohydrate reactant, or is used in combination with otherreducing sugars and/or a polysaccharide, aldotetrose sugars, such aserythrose and threose; and ketotetrose sugars, such as erythrulose, maybe utilized. When a pentose serves as the carbohydrate reactant, or isused in combination with other reducing sugars and/or a polysaccharide,aldopentose sugars, such as ribose, arabinose, xylose, and lyxose; andketopentose sugars, such as ribulose, arabulose, xylulose, and lyxulose,may be utilized. When a hexose serves as the carbohydrate reactant, oris used in combination with other reducing sugars and/or apolysaccharide, aldohexose sugars, such as glucose (i.e., dextrose),mannose, galactose, allose, altrose, talose, gulose, and idose; andketohexose sugars, such as fructose, psicose, sorbose and tagatose, maybe utilized. When a heptose serves as the carbohydrate reactant, or isused in combination with other reducing sugars and/or a polysaccharide,a ketoheptose sugar such as sedoheptulose may be utilized. Otherstereoisomers of such carbohydrate reactants not known to occurnaturally are also contemplated to be useful in preparing the bindercompositions as described herein. In one embodiment, the carbohydratereactant is high fructose corn syrup.

In illustrative embodiments, the carbohydrate reactant is apolysaccharide. In one embodiment, the carbohydrate reactant is apolysaccharide with a low degree of polymerization. In one embodiment,the polysaccharide is molasses, starch, cellulose hydrolysates, ormixtures thereof. In one embodiment, the carbohydrate reactant is astarch hydrolysate, a maltodextrin, or a mixture thereof. Whilecarbohydrates of higher degrees of polymerization may not be preferable,they may none-the-less be useful within the scope of the presentdisclosure by in-situ depolymerization (i.e. depolymerization throughammoniation at elevated temperatures is a method known in the art).

Furthermore, the carbohydrate reactant may be used in combination with anon-carbohydrate polyhydroxy reactant. Examples of non-carbohydratepolyhydroxy reactants which can be used in combination with thecarbohydrate reactant include, but are not limited to,trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol,partially hydrolyzed polyvinyl acetate, fully hydrolyzed polyvinylacetate, and mixtures thereof. In one aspect, the non-carbohydratepolyhydroxy reactant is sufficiently nonvolatile to maximize its abilityto remain available for reaction with a monomeric or polymericpolyamine. It is appreciated that the hydrophobicity of thenon-carbohydrate polyhydroxy reactant may be a factor in determining thephysical properties of a binder prepared as described herein.

As used herein, a polyamine is an organic compound having two or moreamine groups. As used herein, a primary polyamine is an organic compoundhaving two or more primary amine groups (—NH₂). Within the scope of theterm primary polyamine are those compounds which can be modified in situor isomerize to generate a compound having two or more primary aminegroups (—NH₂). In illustrative embodiments, the polyamine is a primarypolyamine. In one embodiment, the primary polyamine may be a moleculehaving the formula H₂N-Q-NH₂, wherein Q is an alkyl, cycloalkyl,heteroalkyl, or cycloheteroalkyl, each of which may be optionallysubstituted. In one embodiment, Q is an alkyl selected from a groupconsisting of C₂-C₂₄. In another embodiment, Q is an alkyl selected froma group consisting of C₂-C₈. In another embodiment, Q is an alkylselected from a group consisting of C₃-C₇. In yet another embodiment, Qis a C₆ alkyl. In one embodiment, Q is selected from the groupconsisting of a cyclohexyl, cyclopentyl or cyclobutyl. In anotherembodiment, Q is a benzyl.

As used herein, the term “alkyl” includes a chain of carbon atoms, whichis optionally branched. As used herein, the term “alkenyl” and “alkynyl”includes a chain of carbon atoms, which is optionally branched, andincludes at least one double bond or triple bond, respectively. It is tobe understood that alkynyl may also include one or more double bonds. Itis to be further understood that alkyl is advantageously of limitedlength, including C₁-C₂₄, C₁-C₁₂, C₁-C₈, C₁-C₆, and C₁-C₄. It is to befurther understood that alkenyl and/or alkynyl may each beadvantageously of limited length, including C₂-C₂₄, C₂-C₁₂, C₂-C₈,C₂-C₆, and C₂-C₄. It is appreciated herein that shorter alkyl, alkenyl,and/or alkynyl groups may add less hydrophilicity to the compound andaccordingly will have different reactivity towards the carbohydratereactant and solubility in a binder solution.

As used herein, the term “cycloalkyl” includes a chain of carbon atoms,which is optionally branched, where at least a portion of the chain incyclic. It is to be understood that cycloalkylalkyl is a subset ofcycloalkyl. It is to be understood that cycloalkyl may be polycyclic.Illustrative cycloalkyls include, but are not limited to, cyclopropyl,cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyleth-2-yl,adamantyl, and the like. As used herein, the term “cycloalkenyl”includes a chain of carbon atoms, which is optionally branched, andincludes at least one double bond, where at least a portion of the chainin cyclic. It is to be understood that the one or more double bonds maybe in the cyclic portion of cycloalkenyl and/or the non-cyclic portionof cycloalkenyl. It is to be understood that cycloalkenylalkyl andcycloalkylalkenyl are each subsets of cycloalkenyl. It is to beunderstood that cycloalkyl may be polycyclic. Illustrative cycloalkenylinclude, but are not limited to, cyclopentenyl, cyclohexylethen-2-yl,cycloheptenylpropenyl, and the like. It is to be further understood thatchain forming cycloalkyl and/or cycloalkenyl is advantageously oflimited length, including C₃-C₂₄, C₃-C₁₂, C₃-C₈, C₃-C₆, and C₅-C₆. It isappreciated herein that shorter alkyl and/or alkenyl chains formingcycloalkyl and/or cycloalkenyl, respectively, may add less lipophilicityto the compound and accordingly will have different behavior.

As used herein, the term “heteroalkyl” includes a chain of atoms thatincludes both carbon and at least one heteroatom, and is optionallybranched. Illustrative heteroatoms include nitrogen, oxygen, and sulfur.In certain variations, illustrative heteroatoms also include phosphorus,and selenium. In one embodiment, a heteroalkyl is a polyether. As usedherein, the term “cycloheteroalkyl” including heterocyclyl andheterocycle, includes a chain of atoms that includes both carbon and atleast one heteroatom, such as heteroalkyl, and is optionally branched,where at least a portion of the chain is cyclic. Illustrativeheteroatoms include nitrogen, oxygen, and sulfur. In certain variations,illustrative heteroatoms also include phosphorus, and selenium.Illustrative cycloheteroalkyl include, but are not limited to,tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl,morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl, and the like.

The term “optionally substituted” as used herein includes thereplacement of hydrogen atoms with other functional groups on theradical that is optionally substituted. Such other functional groupsillustratively include, but are not limited to, amino, hydroxyl, halo,thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl,nitro, sulfonic acids and derivatives thereof, carboxylic acids andderivatives thereof, and the like. Illustratively, any of amino,hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl,arylheteroalkyl, and/or sulfonic acid is optionally substituted.

In illustrative embodiments, the primary polyamine is a diamine,triamine, tetraamine, or pentamine. In one embodiment, the polyamine isa triamine selected a diethylenetriamine, 1-piperazineethaneamine, orbis(hexamethylene)triamine. In another embodiment, the polyamine is atetramine, for example triethylenetetramine. In another embodiment, thepolyamine is a pentamine, for example tetraethylenepentamine.

One aspect of the primary polyamine is that it may possess low sterichindrance. For example, 1,2-diaminoethane, 1,4-diaminobutane,1,5-diaminopentane, 1,6-diaminohexane, 1,12-diaminododecane,1,4-diaminocyclohexane, 1,4-diaminobenzene, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, 1-piperazineethaneamine,2-methyl-pentamethylenediamine, 1,3-pentanediamine, andbis(hexamethylene)triamine, as well as 1,8-diaminooctane have low sterichindrance within the scope of the present disclosure. One embodiment is1,6-diaminohexane (hexamethylenediamine). Another embodiment is1,5-diamino-2-methylpentane (2-methyl-pentamethylenediamine). In anotherembodiment, the primary polyamine is a polyether-polyamine. In anotherembodiment, the polyether-polyamine is a diamine or a triamine. In oneembodiment, the polyether-polyamine is a trifunctional primary aminehaving an average molecular weight of 440 known as Jeffamine T-403Polyetheramine (Huntsman Corporation).

In one embodiment, the polyamine may include a polymeric polyamine. Forexample, polymeric polyamines within the scope of the present disclosureinclude chitosan, polylysine, polyethylenimine, poly(N-vinyl-N-methylamine), polyaminostyrene and polyvinylamines. In one embodiment, thepolyamine comprises a polyvinyl amine. As used herein, the polyvinylamine can be a homopolymer or a copolymer.

While not limited to a particular theory, one aspect of the presentdisclosure is that the primary polyamine and the carbohydrate reactantare Maillard reactants that react to form a melanoidin product. FIG. 1shows a schematic of a Maillard reaction, which culminates in theproduction of melanoidins. In its initial phase, a Maillard reactioninvolves a carbohydrate reactant, for example, a reducing sugar (notethat the carbohydrate reactant may come from a substance capable ofproducing a reducing sugar under Maillard reaction conditions). Thereaction also involves condensing the carbohydrate reactant (e.g.,reducing sugar) with an amine reactant, i.e., a compound possessing anamino group. In other words, the carbohydrate reactant and the aminereactant are the melanoidin reactants for a Maillard reaction. Thecondensation of these two constituents produces an N-substitutedglycosylamine. For a more detailed description of the Maillard reactionsee, Hodge, J. E. Chemistry of Browning Reactions in Model Systems J.Agric. Food Chem. 1953, 1, 928-943, the disclosure of which is herebyincorporated herein by reference. The literature on Maillard reactionsfocuses on a melanoidins produced from amino acids. The presentdisclosure can be distinguished from these references in that not allamino acids are polyamines. Common amino acids which are consideredpolyamines within the scope of the present disclosure includeasparagine, glutamine, histidine, lysine, and arginine.

Without being bound to theory, the covalent reaction between thepolyamine and the carbohydrate reactant will be described in greaterspecificity. As described herein, the pathway of the present reaction isdistinct from those taught in the prior art for the following reasons:(1) the present reaction may occur completely at basic pH, (2) thepolyamine is di-functional in its reactivity towards the carbohydratereactant, (3) the polyamine, through its di-functional reactivity oranother unrecognized phenomena, exhibits a lower activation energywithin the scope of the reaction which results in an unexpected increasein reaction rate and/or a decrease in the temperature at which thereaction will proceed.

The first step in the formation of melanoidins from a polyamine and acarbohydrate reactant is the condensation of the carbohydrate reactantand the polyamine. Evidence indicates that the conditions describedherein are especially suitable for driving this reaction to completion.First, it is believed that the alkalinity of the binder solution drivesthe condensation. For example, it has been shown that sugars and aminesundergo browning in aqueous solution in proportion to the basic strengthof the amines employed or the pH of the solution. It is believed thatthe N-substituted glycosylamines remain undissociated in aqueoussolutions to appreciable extents. Thus, the irreversible transformationsthat the undissociated molecules undergo must be considered. While it isknown that the condensation reaction is reversible, we discovered thatthis reaction can be further driven to completion, in accordance with LeChatelier's principle by the concurrent dehydration of the bindersolution. As such, it was established that initially a primaryconstituent of the uncured binder composition was the N-glycosylderivatives of the primary polyamines.

Referring again to FIG. 1 , the second step in the conversion of thebinder reactants to melanoidin products is the so-called Amadorirearrangement. A schematic of a representative Amadori rearrangement isshown in FIG. 2 . Referring to FIG. 2 , the N-glycosyl derivatives ofthe primary polyamines are in equilibrium with the cation of a Schiffbase. While this equilibrium favors the N-glycosylamine, furtherrearrangement of the cation of a Schiff base to the enol or keto form isknown to proceed spontaneously. It was discovered that this spontaneousreaction is further facilitated by dehydration, as the rate wasincreased in dehydrated samples. One aspect of the present disclosure isthat the structure of a primary polyamine specifically accelerates thisrearrangement by stabilizing the positive charge that is acquired whilethe compound is in the form of a cation of a Schiff base. It is believedthat this stabilization effect has not been discussed in the prior artor the literature as the enhanced effect of using a primary polyaminehas not previously been disclosed. Accordingly, one aspect of thepresent disclosure is that the primary polyamine is of a type thatprovides stability to a cation of a Schiff base during an Amodorirearrangement. In another aspect, the primary polyamine is of a typethat provides stability to a cation of a Schiff base during an Amadorirearrangement while in a substantially dry state. v

Another aspect of the present disclosure is that the carbohydratestructure is also believed to influence the kinetics of the Amadorirearrangement. Specifically, it is known when the C-2 hydroxyl of acrystalline N-substituted glycosylamine was unsubstituted, the compoundwas slowly transformed during storage to the Amadori rearrangementproduct. However, if the C-2 hydroxyl was substituted, then therearrangement was substantially inhibited. Accordingly, one aspect ofthe present disclosure is that a carbohydrate of the present disclosureis unsubstituted at the C-2 hydroxyl. One aspect of the presentdisclosure is that the uncured binder composition comprises a mixture ofN-glycosylamines, 1-amino-1-deoxy-2-ketoses in their enol- andketo-form. Referring again to FIG. 1 , after the formation of themixture of N-glycosylamines, 1-amino-1-deoxy-2-ketoses in their enol-and keto-form the mixture will also include a non-negligibleconcentration of both the un-reacted primary polyamine and thecarbohydrate. From then, a number of reactions may occur which lead towhat can be broadly described as melanoidins. Depending on the identityof both the carbohydrate reactant and polymeric polyamine and thereaction conditions (pH, temperature, oxygen levels, humidity, andpresence of additives) one or more of the shown reaction pathways shownin FIG. 1 may be favored. Furthermore, the favored reaction pathway fora given melanoidin product may not be classifiable as any of those shownspecifically in FIG. 1 .

In illustrative embodiments, the weight ratio of the carbohydratereactant to the primary polyamine is in the range of about 1:1 to about30:1. In another embodiment, the weight ratio of the carbohydratereactant to the primary polyamine is in the range of about 2:1 to about10:1. In yet another embodiment, the weight ratio of the carbohydratereactant to the primary polyamine is in the range of about 3:1 to about6:1. According to one aspect, the cure rate is a function of the weightratio of the carbohydrate reactant to the primary polyamine. Accordingto this function, it was established that as the ratio decreased, thecure rate increased; thus the cure time decreased. Accordingly, the oneaspect of the present disclosure is that the cure time is directlyrelated to the weight ratio of the carbohydrate reactant to thepolyamine provided that other parameters are held equivalent. In anotheraspect, the binder cure time is reduced to the cure time of a comparablephenol formaldehyde binder composition when the weight ratio of thecarbohydrate reactant to the primary polyamine is equal to about 6:1.Accordingly, in one embodiment, a binder according to the presentdisclosure has a cure rate exceeding a comparable phenol formaldehydebinder system when the carbohydrate reactant to primary polyamine weightratio is in the range of about 2:1 to about 6:1.

Another aspect of the reaction as described herein is that, initially,the aqueous reactant solution (which may be dehydrated and used as abinder), as described above, has an alkaline pH. One aspect of thepresent disclosure is that the alkaline binder solution is lesscorrosive towards metal than acidic solution. Accordingly, one featureof the present disclosure which overcomes a substantial barrier to theindustry is that the binder described herein has low corrosivity towardsthe manufacturing equipment which may be used to produce materials whichinclude the present binder because of the alkaline binder composition.One distinguishing feature of the present disclosure over other recentlydescribed carbohydrate binder systems (e.g. U.S. Published ApplicationNo. 2007/0027283), is that the reaction does not necessarily proceedthrough an acidic pathway. Rather, one aspect of the present disclosureis that the uncured binder may have an alkaline pH throughout the courseof the chemical reaction which leads to the formation of the curedbinder. As such, the uncured binder, throughout its use and storage doesnot present a corrosion risk. In illustrative embodiments, an aqueousextract of the cured binder has a pH in the range of about 5 to about 9.Furthermore, an aqueous extract of the polymeric product is essentiallycolorless.

In illustrative embodiments, a method of making a collection of matterbound with a polymeric binder comprises preparing a solution containingreactants for producing the polymeric binder and a solvent, wherein thereactants include a carbohydrate reactant and a polyamine; disposing thesolution onto the collection of matter; volatilizing the solvent to forman uncured product, and subjecting the uncured product to conditionsthat cause the carbohydrate reactant and the polyamine to polymerize toform the polymeric binder.

In illustrative embodiments, the collection of matter includesinsulating fibers. In one embodiment, a fiber insulation product isdescribed which includes insulating fibers and a binder. As used herein,the term “insulating fiber,” indicates heat-resistant fibers suitablefor withstanding elevated temperatures. Examples of such fibers include,but are not limited to, mineral fibers (glass fibers, slag wool fibers,and rock wool fibers), aramid fibers, ceramic fibers, metal fibers,carbon fibers, polyimide fibers, certain polyester fibers, and rayonfibers. Illustratively, such fibers are substantially unaffected byexposure to temperatures above about 120° C. In one embodiment, theinsulating fibers are glass fibers. In yet another embodiment, themineral fibers are present in the range from about 70% to about 99% byweight.

In illustrative embodiments, the collection of matter includescellulosic fibers. For example, the cellulosic fibers may be woodshavings, sawdust, wood pulp, or ground wood. In yet another embodiment,the cellulosic fibers may be other natural fibers such as jute, flax,hemp, and straw. The binder disclosed herein may be used as in the placeof the binder described in Published PCT application WO 2008/089847,which is incorporated herein by reference in its entirety. In oneembodiment, a composite wood board comprising wood particles and abinder is disclosed. In another embodiment, the composite wood board isformaldehyde free. In one embodiment, the composite wood board has anominal thickness range of greater than 6 mm to 13 mm, and has a modulusof elasticity (MOE) of at least about 1050 N/mm², a bending strength(MOR) of at least about 7 N/mm², and an internal bond strength (IB) ofat least 0.20 N/mm². In another embodiment, the composite wood board hasa nominal thickness range of greater than 6 mm to 13 mm, and has abending strength (MOR) of at least about 12.5 N/mm², and an internalbond strength (IB) of at least 0.28 N/mm². In another embodiment, thecomposite wood board has a nominal thickness range of greater than 6 mmto 13 mm, and has a modulus of elasticity (MOE) of at least about 1800N/mm², a bending strength (MOR) of at least about 13 N/mm², and aninternal bond strength (TB) of at least 0.40 N/mm². In anotherembodiment, the composite wood board has a modulus of elasticity (MOE)of at least about 1800 N/mm². In another embodiment, the composite woodboard has a modulus of elasticity (MOE) of at least about 2500 N/mm². Inanother embodiment, the composite wood board has a bending strength(MOR) of at least about 14 N/mm². In yet another embodiment, thecomposite wood board has a bending strength (MOR) is at least about 18N/mm². In one embodiment, the composite wood board has an internal bondstrength (IB) of at least 0.28 N/mm². In yet another embodiment, thecomposite wood board has an internal bond strength (IB) is at least 0.4N/mm². In yet another embodiment, the composite wood board swells lessthan or equal to about 12%, as measured by a change in thickness, after24 hours in water at 20° C. In another embodiment, the composite woodboard has a water absorption after 24 hours in water at 20° C. of lessthan or equal to about 40%.

In illustrative embodiments the composite wood board is a woodparticleboard, an orientated strandboard, or a medium densityfiberboard. In one embodiment, the binder comprises from about 8% toabout 18% by weight (weight of dry resin to weight of dry woodparticles) of the composite wood board. In another embodiment, thecomposite wood board further comprises a wax. In yet another embodiment,the composite wood board comprises from about 0.1% to about 2% wax byweight of the composite wood board. In illustrative embodiments, themethod of making a collection of matter bound with a polymeric bindermay further include preparing a solution by adding an amount of acarbohydrate reactant and an amount of a primary polyamine so a weightratio is in the range of about 2:1 to about 10:1. In one embodiment,preparing the solution includes adding the carbohydrate reactant and thepolyamine to an aqueous solution. In another embodiment, preparing thesolution includes adjusting the pH of the solution to within the rangeof about 8 to about 12. In yet another embodiment, the method of makinga collection of matter bound with a polymeric binder may furthercomprise packaging the uncured product in a packaging material suitablefor storage.

In illustrative embodiments, the present disclosure relates to acomposition comprising a collection of matter and a binder, the bindercomprising polymeric products of a reaction between a carbohydratereactant and a polyamine, the polymeric products being substantiallywater insoluble. In one embodiment, the collection of matter includesmineral fibers, aramid fibers, ceramic fibers, metal fibers, carbonfibers, polyimide fibers, polyester fibers, rayon fibers, glass fibers,cellulosic fibers or other particulates. For example, cellulosic fibersmay include wood shavings, sawdust, wood pulp, and/or ground wood. Inone embodiment, the collection of matter includes sand or otherinorganic particulate matter. In one embodiment, the collection ofmatter is coal particulates. In one embodiment, the carbohydratereactant is selected from a group consisting of dextrose, xylose,fructose, dihydroxyacetone, and mixtures thereof. In one embodiment, thepolyamine is selected from any of the polyamines described hereinabove.In another embodiment, the polyamine is selected from a group consistingof a diamine, triamine, tetramine, and pentamine. In one embodiment, thepolyamine is H₂N-Q-NH₂, wherein Q is alkyl, cycloalkyl, heteroalkyl, orcycloheteroalkyl, each of which is optionally substituted. In anotherembodiment, the composition further comprises a silicon-containingcompound. In one embodiment the silicon-containing compound is afunctionalized silylether or a functionalized alkylsilylether, such asfor example, an amino-functionalized alkylsilylether. For example, inone embodiment, the silicon-containing compound may begamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane,or aminoethylaminopropyltrimethoxysilane, or a mixture thereof. Inanother embodiment, the silicon-containing compound may be anaminofunctional oligomeric siloxane. In another embodiment, thecomposition comprises a corrosion inhibitor selected from a groupconsisting of dedusting oil, monoammonium phosphate, sodium metasilicatepentahydrate, melamine, tin (II)oxalate, and a methylhydrogen siliconefluid emulsion.

In further illustrative embodiments, the binder may be disposed upon acollection of fibers, substantially dehydrated, packaged, and thenstored or sold to another party. An uncured product sold to anotherparty for use in further manufacturing processes may be referred to as“ship-out uncured.” An uncured product stored for use in furthermanufacturing processes may be referred to as “plant uncured.” Inselling or storing this type of product, it is packaged in suitablecontainers or bags.

In illustrative embodiments, a packaged uncured fiber product comprisesan uncured binder composition and a collection of fibers, wherein (i)the uncured binder composition is in contact with the collection offibers consolidating the collection of fibers and (ii) the uncuredbinder composition in contact with the collection of fibers is packagedin a suitable packaging material. In one embodiment, the amount ofmoisture in the uncured binder composition may be in a range from about1% to about 15% by weight based on a total weight of the product. In yetanother embodiment, the suitable packaging material may be capable ofmaintaining the amount of moisture in the uncured binder composition towithin about 20% of an original moisture level for a period of one weekat an ambient temperature and an ambient pressure. In one embodiment,the packaged uncured fiber product comprises from about 3% to about 30%by weight of the uncured binder composition based on weight of thepackaged uncured fiber product without considering the weight of thesuitable packaging material. In one embodiment, the packaged uncuredfiber product comprises from about 60 to about 97% by weight fibersbased on weight of the packaged uncured fiber insulation product withoutconsidering the weight of the suitable packaging material.

One aspect of the present disclosure is that the binder described hereinis unexpectedly useful in applications ship-out uncured and plantuncured applications. Specifically, ship-out uncured products and plantuncured products are provided with an uncured binder so that the curingcan occur at a later time and in a later place. In the case of ship-outuncured, the curing temperature and time are properties of the productwhich are of great importance to the customers. Specifically, the curetemperatures must be sufficiently low such that the product can be curedusing their existing equipment. Furthermore, the cure time must besufficiently short such that the cycle time for curing the productsremains low. Within this industry, the manufacturing equipment andacceptable cycle times have been established for uncured productscomprising phenol formaldehyde type resins. Therefore, sufficiently lowcure temperatures are those cure temperatures suitable for curing acomparable phenol formaldehyde type product. Similarly, sufficiently lowcycle times are those cycle times which would be routine for curing acomparable phenol formaldehyde type product. One of ordinary skill inthe art will appreciate that neither cure time nor cure temperature canbe set forth as definite quantities because the specific applicationsmay have dramatically different parameters. However, it is wellunderstood that the cure time and cure temperatures of a model systemprovide sufficient representative information regarding the kinetics ofthe underlying chemical curing reaction so that reliable predictions ofbinder performance in the various applications can be made.

In illustrative embodiments, the cure time and the cure temperature ofthe binder is equal to or less than a comparable phenol formaldehydebinder composition. In one embodiment, the cure time of the binder isless than the cure time of a comparable phenol formaldehyde bindercomposition. In another embodiment, the cure temperature of the binderis less than the cure temperature of a comparable phenol formaldehydebinder composition. As used herein, a comparable phenol formaldehydebinder composition is like that described according to U.S. Pat. No.6,638,882, which patent is hereby incorporated by reference herein inits entirety.

As discussed below, various additives can be incorporated into thebinder composition. These additives give the binders of the presentinvention additional desirable characteristics. For example, the bindermay include a silicon-containing coupling agent. Many silicon-containingcoupling agents are commercially available from the Dow-CorningCorporation, Evonik Industries, and Momentive Performance Materials.Illustratively, the silicon-containing coupling agent includes compoundssuch as silylethers and alkylsilyl ethers, each of which may beoptionally substituted, such as with halogen, alkoxy, amino, and thelike. In one variation, the silicon-containing compound is anamino-substituted silane, such as, gamma-aminopropyltriethoxy silane(SILQUEST A-1101; Momentive Performance Materials, CorporateHeadquarters: 22 Corporate Woods Boulevard, Albany, NY 12211 USA). Inanother variation, the silicon-containing compound is anamino-substituted silane, for example, aminoethylaminopropyltrimethoxysilane (Dow Z-6020; Dow Chemical, Midland, MI; USA). In anothervariation, the silicon-containing compound isgamma-glycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive). Inyet another variation, the silicon-containing compound is anaminofunctional oligomeric siloxane (HYDROSIL 2627, Evonik Industries,379 Interpace Pkwy, Parsippany, NJ 07054).

The silicon-containing coupling agents are typically present in thebinder in the range from about 0.1 percent to about 1 percent by weightbased upon the dissolved binder solids (i.e., about 0.05% to about 3%based upon the weight of the solids added to the aqueous solution). Inone application, one or more of these silicon-containing compounds canbe added to the aqueous binder solution. The binder is then applied tothe material to be bound. Thereafter, the binder may be cured ifdesired. These silicone containing compounds enhance the ability of thebinder to adhere to the matter the binder is disposed on, such as glassfibers. Enhancing the binder's ability to adhere to the matter improves,for example, its ability to produce or promote cohesion in non- orloosely-assembled substance(s).

In another illustrative embodiment, a binder of the present inventionmay include one or more corrosion inhibitors. These corrosion inhibitorsprevent or inhibit the eating or wearing away of a substance, such as,metal caused by chemical decomposition brought about by an acid. When acorrosion inhibitor is included in a binder of the present invention,the binder's corrosivity is decreased as compared to the corrosivity ofthe binder without the inhibitor present. In one embodiment, thesecorrosion inhibitors can be utilized to decrease the corrosivity of themineral fiber-containing compositions described herein. Illustratively,corrosion inhibitors include one or more of the following, a dedustingoil, or a monoammonium phosphate, sodium metasilicate pentahydrate,melamine, tin(II) oxalate, and/or methylhydrogen silicone fluidemulsion. When included in a binder of the present invention, corrosioninhibitors are typically present in the binder in the range from about0.5 percent to about 2 percent by weight based upon the dissolved bindersolids. One aspect of the present disclosure is that the need forcorrosion inhibiting additives is greatly reduced by the alkalinity ofthe binder solution and the substantially dehydrated uncured binder. Inone embodiment, the binder is free from corrosion inhibitors and thecorrosivity of the binder solution is within the acceptable range.

In illustrative embodiments, the binder may further include anon-aqueous moisturizer. The non-aqueous moisturizer may include one ormore polyethers. For example, the non-aqueous moisturizer may include anethylene oxide or propylene oxide condensates having straight and/orbranched chain alkyl and alkaryl groups. In one embodiment, thenon-aqueous moisturizer includes a polyethylene glycol, a polypropyleneglycol ether, a thioether, a polyoxyalkylene glycol (e.g., JeffoxTP400®), a dipropylene glycol, and/or a polypropylene glycol (e.g.,Pluriol P425® or Pluriol 2000®). In one embodiment, the non-aqueousmoisturizer comprises a polyoxyalkylene glycol or a polypropyleneglycol. In another embodiment, the non-aqueous moisturizer includes acompound based on a polyhydroxy compound (e.g., a partially or fullyesterified polyhydroxy compound). In another embodiment, the non-aqueousmoisturizer includes a polyhydroxy based on a glycerine, a propyleneglycol, an ethylene glycol, a glycerine acetate, a sorbitol, a xylitolor a maltitol.

In another embodiment, the non-aqueous moisturizer includes othercompounds having multiple hydroxyl groups based on tetrahydrofuran, acaprolactone, and/or a alkylphenoxypoly(ethyleneoxy)ethanols havingalkyl groups containing from about 7 to about 18 carbon atoms and havingfrom about 4 to about 240 ethyleneoxy units. For example, thenon-aqueous moisturizer may include aheptylphenoxypoly(ethyleneoxy)ethanol and/or anonylphenoxypoly(ethyleneoxy)ethanol. In another embodiment, thenon-aqueous moisturizer includes a polyoxyalkylene derivative of hexitolsuch as a sorbitan, sorbide, mannitan, and/or a mannide. In yet anotherembodiment, the non-aqueous moisturizer may include a partial long-chainfatty acids ester, such as a polyoxyalkylene derivative of sorbitanmonolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitantristearate, sorbitan monooleate, and/or sorbitan trioleate.

In illustrative embodiments, the non-aqueous moisturizer includes acondensate of ethylene oxide with a hydrophobic base, the base beingformed by condensing propylene oxide with propylene glycol. In oneembodiment, the non-aqueous moisturizer includes a sulfur containingcondensate, such as those prepared by condensing ethylene oxide with ahigher alkyl mercaptan (e.g., nonyl, dodecyl, tetradecyl mercaptan, oralkylthiophenols having about 6 to about 15 carbon atoms in the alkylgroup). In another embodiment, the non-aqueous moisturizer includes anethylene oxide derivative of a long-chain carboxylic acid, such aslauric, myristic, palmitic, or oleic acids. In yet another embodiment,the non-aqueous moisturizer includes an ethylene oxide derivative of along-chain alcohol such as octyl, decyl, lauryl, or cetyl alcohols. Inanother embodiment, the non-aqueous moisturizer includes an ethyleneoxide/tetrahydrofuran copolymer or an ethylene oxide/propylene oxidecopolymer.

The following examples illustrate specific embodiments in furtherdetail. These examples are provided for illustrative purposes only andshould not be construed as limiting the invention or the inventiveconcept to any particular physical configuration in any way.

EXAMPLES Example 1

A solution of 50 g dextrose (0.278 mol), 50 g hexamethylenediamine(0.431 mol) dissolved in 566.6 g deionized water (15% solids solution,pH 11.9) was heated to the boiling point of the solution. A brownishwater insoluble polymer was observed as a precipitate in the reactionvessel.

Example 2

From the above solution of 50 g dextrose (0.278 mol), 50 ghexamethylenediamine (0.431 mol) dissolved in 566.6 g deionized water(15% solids solution, pH 11.9), 2 g of the binder solution was appliedon a filter pad which is placed in a Moisture Balance and heated for 15min at 120° C. A brownish water insoluble polymer formed on the filterpad. An extraction of the cured filter pad using 100 g of deionizedwater is essentially colorless and has a pH of 6.8.

Example 3

A solution of 85 g dextrose (0.472 mol), 15 g hexamethylenediamine(0.129 mol) dissolved in 566.6 g deionized water (15% solids solution,pH 10.8) was prepared. 2 g of the binder solution was applied on afilter pad which is placed in a Moisture Balance and heated for 15 minat 140° C. A brownish water insoluble polymer formed on the filter pad.An extraction of the cured filter pad using 100 g of deionized water isessentially colorless and has a pH of 6.8.

Example 4

A solution of 95 g dextrose (0.528 mol), 5 g hexamethylenediamine (0.043mol) dissolved in 566.6 g deionized water (15% solids solution) wasprepared. 2 g of the binder solution was applied on a filter pad whichis placed in a Moisture Balance and heated for 15 min at 180° C. Abrownish water insoluble polymer formed on the filter pad. An extractionof the cured filter pad using 100 g of deionized water is essentiallycolorless and has a pH of 6.8.

Comparative Example 1

A solution of 180 g dextrose (1 mol) dissolved in 1020 g deionized water(15% solids solution) was prepared. 2 g of the binder solution wasapplied on a filter pad which is placed in a Moisture Balance and heatedfor 15 min at 180° C. A water insoluble polymer was not formed on thefilter pad. The resulting heat treated binder was essentially fullywater soluble.

Cure Rate and Cure Time: Square Fiberglass mats (13″×13″) with a weightof 44 g (corresponding to 34.5 g/ft²) were impregnated with a bindercontaining 15% solids. Excess of binder is removed by vacuum suction,and the moist mat is dried for at least 12 hours at 90° F. in an oven(recirculation).

The dried mat is cut in four squares of the same dimension. The squaresare stacked on top of each other, and at least one thermocoupleconnected to a recorder (i.e. oven mole) is placed in the middle of thestack between the 2^(nd) and 3^(rd) layer.

A mold press with temperature controlled platen is heated to 400° F.(204° C.). The sample with the prepared thermocouple is placed in themiddle of the platen, and pressed to a thickness of ⅝″ for a predefinedtime (i.e. 3.5 min, 4.0 min, 5.0 min, 6.0 min, 15 min).

Each molded sample was evaluated for the degree of cure by testingevenness of the surfaces, water hold-up, and extract. A sample wasdeemed to be cured when the surfaces are smooth without any “bumps”, thesample does not noticeably weaken when immersed in water, and nosignificant extract color is formed when immersing the sample in water.The temperature profile of the center of the sample is measured duringthe molding cycle and is shown in FIG. 3 .

Comparative Example 2: Phenol Formaldehyde Binder

Composition based on dry solids:

-   -   2.41 parts Ammonium Sulfate    -   1.08 part of Ammonia    -   0.21 parts Silane A1101    -   96.3% phenol formaldehyde-Resin:Urea Premix (70:30)        Comparative Example 2 is referred to as Binder 1 within FIG. 3 .

Comparative Example 3: Carbohydrate-Inorganic Acid Binder

Composition based on dry solids:

-   -   81.59 parts Dextrose    -   17.09 parts Ammonium Sulfate    -   1 part of Ammonia    -   0.3 parts Silane A1101        Comparative Example 3 is referred to as Binder 2 within FIG. 3 .

Example 5

Composition based on dry solids:

-   -   80.94 parts Dextrose and Ammonia solution (an aqueous solution        containing 2 mol/liter Dextrose and 2 mol/liter Ammonia)    -   19.06 parts Hexamethylenediamine        Example 5 is referred to as Binder 4 within FIG. 3 .

It was determined that the time required to achieve full cure of abinder within the scope of the present disclosure is less than that of 3comparative example binder systems having diverse chemistries. Thismodel system illustrates that the cure time, providing that othervariables are kept constant, is dependent on the chemistry of the bindersystem. The chemistry of an illustrative binder composition within thescope of the present disclosure achieves improved cure times incomparison to these other exemplary systems. The results are shownfollowing:

Binder Molding Time to achieve full cure Comparative Ex. 2 - Binder 1Minimum of 240 seconds Comparative Ex. 3 - Binder 2 Minimum of 300seconds Ex. 5 - Binder 4 Cured at 210 seconds

Referring now to FIG. 3 , shown is the temperature profilecharacteristic for each of binders 1, 2, and 4. It was noted that thetemperature profile is characteristic for each binder. It was notestablished that the cure rate and cure time is not characteristic ofthe cure temperature profile. However, the cure temperature profilehelps to understand and predict cure rate and cure time. Specifically,Comparative Example 3 required the greatest cure time; and, similarly,the cure temperature profile required the greatest amount of time toasymptotically maximize. Similarly, Example 5 required the least amountof time to asymptotically maximize and demonstrated the shortest curetime.

Carbohydrate Reactant: Polyamine Ratio Effect on Cure Cycle Time. WetLaid Mats (WLM) were made with varying ratios of dextrose monohydrate(DMH) to Hexamethylenediamine (HMDA). The weight ratios tested include75/25, 85/15, and 92/8 respectively.

A 15% Dextrose-HMDA Binder was applied to 5 WLM's. The following bindercompositions were prepared:

Example 6 Example 7 Example 8 DMH/HMDA 75/25 DMH/HMDA 85/15 DMH/HMDA92/8 Water 1677.45 g 1677.45 g 1677.45 g DMH  246.78 g  279.68 g  302.72g HMDA  74.77 g  44.86 g  23.93 g Silane   1.00 g   1.00 g   1.00 g

The mats are prepared in 13″×13″ pieces, with a thickness of ⅜″. Thepress used to mold the mats is set at 400° F. Once the sample is moldedit is approximately ⅝″ thick. A temperature profile was first determinedin a 15 minute interval. The next sample was pressed for 4 minutes; thisis the time it takes to cure a comparable phenol formaldehyde bindercomposition (results not shown). The experiments were repeated withvarying cure times until the minimum time required to cure eachcomposition was determined. The extent to which each binder had curedwas determined based on weight. The following results were determined:

Cure Cycle Time Example 6 2:30 min. Example 7   4 min. Example 8   8min.

As described above, comparable phenol formaldehyde based product (e.g.Comparative Example 2) cures with a 4 minute cycle time. Furthermore, acomparable carbohydrate based binder (e.g. Comparative Example 3) cureswith a 5 minute cycle time. These results indicate that a binder withinthe scope of the present disclosure with a carbohydrate reactant toprimary polyamine of 85/15 or lower cures at a comparable or faster ratethan the phenol formaldehyde based product. Further experiments showedthat the cure temperature can be lowered in products having a shortercure time to achieve equivalent cure times at lower temperatures. Theresults obtained agreed in principle to our expectations based on theArrhenius equation.

In addition to those examples described in detail, the followingexamples were made to ensure that the carbohydrate reactant andpolyamine may comprise a wide range of alternatives.

Ex. Polyamine Carbohydrate Reactant Binder Formed  9hexamethylenediamine dextrose Yes 10 ethylenediamine dextrose Yes 11diethylenetriamine dextrose Yes 12 hexamethylenediamine high fructosecorn syrup Yes 13 hexamethylenediamine sucrose Yes 14octamethylenediamine dextrose Yes 15 tetramethylenediamine dextrose YesFurther Dextrose-Polyamine Examples:

Example 16: A suspension of 56.08 g deionized water, 7.15 g dextrosemonohydrate, and 3.5 g 1,12-diaminododecane was acidified with 11 N HClto pH 1.0, and heated to 70° C. under agitation resulting into a clear,colorless solution. The solution forms a thermoset, water insolublepolymer at 160° C. (Test condition: 2 g binder solution is applied on afilter pad which is placed in a Moisture Balance. The filter pad isheated for 15 min at 160° C.) An extract of the cured filter pad with100 g of deionized water is essentially colorless.

Example 17: A solution of 8.25 g dextrose monohydrate, and 2.50 g1,5-diamino-2-methylpentane (Dytek A, Invista) dissolved in 56.08 gdeionized water forms a thermoset, water insoluble polymer at 160° C.(Test condition: 2 g binder solution is applied on a filter pad which isplaced in a Moisture Balance. The filter pad is heated for 15 min at160° C.) An extract of the cured filter pad with 100 g of deionizedwater is essentially colorless.

Example 18: A solution of 8.03 g dextrose monohydrate, and 2.70 gN-(3-aminopropyl)-1,3-propanediamine dissolved in 56.08 g deionizedwater forms a thermoset, water insoluble polymer at 200° C. (Testcondition: 2 g binder solution is applied on a filter pad which isplaced in a Moisture Balance. The filter pad is heated for 15 min at200° C.) An extract of the cured filter pad with 100 g of deionizedwater has a slight yellowish color.

Example 19: A solution of 1.0 g dextrose (5.55 mmol), 1.0 g (approx.2.27 mmol) Jeffamine T-403 Polyetheramine dissolved in 8.5 g deionizedwater (19% solids solution) was prepared. 2 g of the binder solution wasapplied on a filter pad which is placed in a Moisture Balance and heatedfor 5 min at 180° C. A brownish water insoluble polymer formed on thefilter pad. An extraction of the cured filter pad using 100 g ofdeionized water is essentially colorless and has a pH of 7.1.

Jeffamine T-403 Polyetheramine is a trifunctional primary amine havingan average molecular weight of 440. Its amine groups are located onsecondary carbon atoms at the ends of aliphatic polyether chains. Itsstructure may be represented as follows, in which the sum of x, y, and zis 6:

Procedure for analyzing a binder sample with gas pyrolysis.Approximately 10 g of a cured product having the binder thereon isplaced in a test tube, which tube is then heated to 1000° F. for 2.5minutes at which time the headspace is sampled and analyzed by gaschromatography/mass spectrometry (GC/MS) under the following conditions:Oven, 50° C. for one minute-10° C./minute to 300° C. for 10 minutes;Inlet, 280° C. splitless; Column, HP-5 30 mm×0.32 mm×0.25 um; Columnflow, 1.11 mL/minute Helium; Detector, MSD 280° C.; Injection volume, 1mL; Detector mode, scan 34-700 amu; Threshold, 50; and Sampling Rate, 22scans/second. A computer search of the mass spectrum of achromatographic peak in the sample is made against the Wiley library ofmass spectra. The best match is reported. A quality index (closeness ofmatch to the library spectra) ranging from 0 to 99 is generated. Onlythe identity of peaks with a quality index of greater than or equal to90 is reported.

The following table provides representative pyrolysis data that oneexpects from the GC/MS analysis of gaseous compounds produced duringpyrolysis of a melanoidin based binder composition.

Retention Time (min) Tentative Identification % Peak Area 1.152-cyclopenten-1-one 10.67  1.34 2,5-dimethyl-furan 5.84 3.54 furan 2.153.60 3-methyl-2,5-furandione 3.93 4.07 phenol 0.38 4.892,3-dimethy1-2-cyclopenten-1-one 1.24 5.11 2-methyl phenol 1.19 5.424-methyl phenol 2.17 6.46 2,4-dimethyl-phenol 1.13 10.57dimethylphthalate 0.97 17.89 octadecanoic acid 1.00 22.75 erucylamide9.72

Following is a listing of the species observed in the pyrolysis gaschromatography mass spectrometry (Py GC-MS) of a binder sample preparedusing hexamethylenediamine as the polyamine component. The pyrolysis wascarried out at 200° C., 300° C., and 770° C. Fingerprinting shows a verysignificant peak which corresponds to acetic acid in the masschromatogram at both 200° C. and 300° C., which was not seen in a samplemade using dextrose and ammonium sulfate (see Comparative Example 3), inwhich the significant volatile was SO₂, particularly at 300° C. At 770°C., the peaks observed, in order of increasing retention time wereassigned as follows: A: Co-eluting C₅H₁₀, C₅H₁₂, acetone, possibly lowmw acetic acid ester; B: C₅H₈ diene; C: C₅H₈ diene; D: likely apentanol; E: C₆H₁₂—a methyl pentene; F: hexane; G: methylcyclopentane;H: a cyclohexadiene; I: C₆H₁₀—probably a methylcyclopentane; J: benzene;K: acetic acid; L: cyclohexene; M: probably nonanol; N:2-methyl-3-pentanone; O: 2,5-dimethylfuran; P: C₇H₁₀+unassignedco-elute; Q: pyridine+unassigned co-elute; R: toluene; S: possiblydecenal+unassigned co-elute; T: 2-ethyl-5-methylfuran; U: a methylpyridine; V: a methyl pyrrole; W: a xylene; X: unassigned—with alcoholfunctionality; Y: unassigned; Z: a xylene+unassigned co-elute; AA:unassigned; AB: a dimethyl pyrrole; AC: a dimethyl pyridine; AD: adimethyl pyridine; AE: unassigned; AF: unassigned; AG: an ethyl methylpyrrole+unassigned co-elute; AI: an unassigned but distinct massspectrum (N-containing), pyrrole related; AJ: an unassigned but distinctmass spectrum (N-containing), possibly an acetamide; AK: an unassignedbut distinct mass spectrum (N-containing), pyrrole related; AL: anunassigned but distinct mass spectrum (N-containing), pyrrole related;AM: an unassigned but distinct mass spectrum (N-containing), pyrrolerelated. The distinct mass spectra seen from peaks AI to AM are not seenin the data of prior binders not having the polyamine component.

Procedure for evaluating dry and weathered tensile strength. Whenevaluated for their dry and “weathered” tensile strength, glassbead-containing shell bone compositions prepared with a given binderprovide an indication of the likely tensile strength and the likelydurability, respectively, of a fiberglass product prepared with thatparticular binder. Predicted durability is based on a shell bone'sweathered tensile strength: dry tensile strength ratio. Shell bones areprepared, weathered, and tested as follows, for example, for ahexamethylenediamine-dextrose binder mixture.

A shell bone mold (Dietert Foundry Testing Equipment; Heated ShellCuring Accessory, Model 366, and Shell Mold Accessory) is set to adesired temperature, generally 425° F., and allowed to heat up for atleast one hour. While the shell bone mold is heating, approximately 100g of an aqueous binder (generally 15% in binder solids) is prepared(e.g. as described in Example 7). Using a large glass beaker, 727.5 g ofglass beads (Quality Ballotini Impact Beads, Spec. AD, US Sieve 70-140,106-212 micron-#7, from Potters Industries, Inc.) are weighed bydifference. The glass beads are poured into a clean and dry mixing bowl,which bowl was mounted onto an electric mixer stand. Approximately 75 gof aqueous binder is poured slowly into the glass beads in the mixingbowl. The electric mixer is then turned on and the glass beads/bindermixture is agitated for one minute. Using a large spatula, the sides ofthe whisk (mixer) are scraped to remove any clumps of binder, while alsoscraping the edges wherein the glass beads lay in the bottom of thebowl. The mixer is then turned back on for an additional minute, andthen the whisk (mixer) is removed from the unit, followed by removal ofthe mixing bowl containing the glass beads/binder mixture. Using a largespatula, as much of the binder and glass beads attached to the whisk(mixer) as possible are removed and then stirred into the glassbeads/binder mixture in the mixing bowl. The sides of the bowl are thenscraped to mix in any excess binder that might have accumulated on thesides. At this point, the glass beads/hexamethylenediamine-dextrosebinder mixture is ready for molding in a shell bone mold.

The slides of the shell bone mold are confirmed to be aligned within thebottom mold platen. Using a large spatula, a glassbeads/hexamethylenediamine-dextrose binder mixture is then quickly addedinto the three mold cavities within the shell bone mold. The surface ofthe mixture in each cavity is flattened out, while scraping off theexcess mixture to give a uniform surface area to the shell bone. Anyinconsistencies or gaps that existed in any of the cavities are filledin with additional glass beads/hexamethylenediamine-dextrose bindermixture and then flattened out. Once a glassbeads/hexamethylenediamine-dextrose binder mixture is placed into theshell bone cavities, and the mixture is exposed to heat, curing begins.As manipulation time can affect test results, e.g., shell bones with twodifferentially cured layers can be produced; shell bones are preparedconsistently and rapidly. With the shell bone mold filled, the topplaten is quickly placed onto the bottom platen. At the same time, orquickly thereafter, measurement of curing time is initiated by means ofa stopwatch, during which curing the temperature of the bottom platenranged from about 400° F. to about 430° F., while the temperature of thetop platen ranged from about 440° F. to about 470° F. At seven minuteselapsed time, the top platen is removed and the slides pulled out sothat all three shell bones can be removed. The freshly made shell bonesare then placed on a wire rack, adjacent to the shell bone mold platen,and allowed to cool to room temperature. Thereafter, each shell bone islabeled and placed individually in a plastic storage bag labeledappropriately. If shell bones can not be tested on the day they wereprepared, the shell bone-containing plastic bags were placed in adesiccator unit.

Conditioning (Weathering) Procedure for Shell Bones: A Blue M humiditychamber is turned on and then set to provide weathering conditions of90° F. and 90% relative humidity (i.e., 90° F./90% rH). The water tankon the side of the humidity chamber is checked and filled regularly,usually each time it is turned on. The humidity chamber is allowed toreach the specified weathering conditions over a period of at least 4hours, with a day-long equilibration period being typical. Shell bonesto be weathered are loaded quickly (since while the doors are open boththe humidity and the temperature decrease), one at a time through theopen humidity chamber doors, onto the upper, slotted shelf of thehumidity chamber. The time that the shell bones are placed in thehumidity chamber is noted, and weathering is conducted for a period of24 hours. Thereafter, the humidity chamber doors are opened and one setof shell bones at a time are quickly removed and placed individuallyinto respective plastic storage bags, being sealed completely.Generally, one to four sets of shell bones at a time are weathered asdescribed above. Weathered shell bones are immediately taken to theInstron room and tested.

Test Procedure for Breaking Shell Bones: In the Instron room, the shellbone test method is loaded on the 5500 R Instron machine while ensuringthat the proper load cell is installed (i.e., Static Load Cell 5 kN),and the machine is allowed to warm up for fifteen minutes. During thisperiod of time, shell bone testing grips are verified as being installedon the machine. The load cell is zeroed and balanced, and then one setof shell bones is tested at a time as follows: A shell bone is removedfrom its plastic storage bag and then weighed. The weight (in grams) isthen entered into the computer associated with the Instron machine. Themeasured thickness of the shell bone (in inches) is then entered, asspecimen thickness, three times into the computer associated with theInstron machine. A shell bone specimen is then placed into the grips onthe Instron machine, and testing initiated via the keypad on the Instronmachine. After removing a shell bone specimen, the measured breakingpoint is entered into the computer associated with the Instron machine,and testing continued until all shell bones in a set are tested.

Carbohydrate Reactant: Polyamine Ratio Effect on Shell Bone Properties.Shell Bones were made with varying ratios of dextrose monohydrate (DMH)to Hexamethylenediamine (HMDA) with a silane additive (ISIO200) wereexamined as described above, at a test speed of 25 mm/min. The weightratios tested include 90/10, 85/15, 80/20 and 75/25, respectively.

Stress at peak/MNm⁻² Strength Dry Weathered Loss/% 90% DMH+ 10% HMDA+2.954 1.929 34.69 0.3% ISIO200, pH 11.06 85% DMH+ 15% HMDA+ 2.573 2.01721.61 0.3% ISIO200, pH 11.29 80% DMH+ 20% HMDA+ 2.747 2.344 14.68 0.3%ISIO200, pH 11.54 75% DMH+ 25% HMDA+ 2.735 2.073 24.21 0.3% ISIO200, pH11.71

Example: Glass Wool (Fiber Glass) Trials

Comparisons of the qualities of two glucose-hexamethylenediamine binderswith a standard binder in terms of curing and rigidity on a glass woolproduct (Ac+032 100 mm 1200 mm width; 32 kg/m³-15 m/min) were carriedout by measuring the parting strength and density.

-   -   Binder 1: 85% glucose-15% hexamethylenediamine.    -   Binder 2: 90% glucose-10% hexamethylenediamine.

Ordinary Parting Strength (Before Autoclave) and Weathered PartingStrength (After Autoclave) may be measured as described in InternationalPatent Application, Publication Number WO 2008/089851 or WO2009/019235.

Parting Strength on a Standard Binder:

BEFORE AUTOCLAVE AFTER AUTOCLAVE Weight (g) Force (N) density (kg/m³)Weight (g) Force (N) density (kg/m³) 1 21.90 72.0 34.5 7 22.00 48.8 34.62 21.00 64.0 33.1 8 21.00 50.7 33.1 3 18.20 51.7 28.7 9 19.80 46.0 31.24 18.80 53.0 29.6 10 17.90 35.6 28.2 5 19.90 50.6 31.3 11 20.10 52.531.7 6 20.40 60.5 32.1 12 19.70 43.9 31.0 Total 120.20 351.8 31.6 Total120.50 277.5 31.6 35861.4 g 28287.5 g P.S. BEFORE: 298.3 gf/gwt P.S.AFTER: 234.8 gf/gwt LOSS: 63.6 gf/gwt ie 21.3%Parting Strength on Binder 1:

BEFORE AUTOCLAVE AFTER AUTOCLAVE Weight (g) Force (N) density (kg/m³)Weight (g) Force (N) density (kg/m³) 1 22.00 95.6 34.6 7 19.8 50.0 31.22 18.70 53.9 29.5 8 17.8 46.7 28.0 3 18.20 63.9 28.7 9 17.8 51.2 28.0 418.10 62.6 28.5 10 20.50 59.3 32.3 5 20.50 75.0 32.3 11 18.40 46.0 29.06 18.70 60.3 29.5 12 18.60 47.3 29.3 Total 116.20 411.3 30.5 Total112.90 300.5 29.6 41926.6 g 30632.0 g P.S. BEFORE: 360.8 gf/gwt P.S.AFTER: 271.3 gf/gwt LOSS: 89.5 gf/gwt ie 24.8%Parting Strength on Binder 2:

BEFORE AUTOCLAVE AFTER AUTOCLAVE Weight (g) Force (N) density (kg/m³)Weight (g) Force (N) density (kg/m³) 1 18.50 51.5 29.1 7 19.40 52.2 30.62 19.50 64.5 30.7 8 20.10 52.7 31.7 3 21.30 75.6 33.5 9 19.30 54.5 30.44 20.80 78.8 32.8 10 19.80 57.2 31.2 5 19.80 64.4 31.2 11 19.80 58.231.2 6 18.40 70.0 29.0 12 18.80 51.9 29.6 Total 118.30 404.8 31.1 Total117.20 326.7 30.8 41264.0 g 33302.8 g P.S. BEFORE: 348.8 gf/gwt P.S.AFTER: 284.2 gf/gwt LOSS: 78.1 gf/gwt ie 19.3%Observations during the trial: The product was browner on the line withthe two glucose-hexamethylenediamine binders.

Conclusions: With the two glucose-hexamethylenediamine binders, theparting strength (which is a longitudinal tensile strength) resultsshowed a significant improvement; and a significant improvement wasobserved in three other rigidity tests (“60°” test-sagging measured whenleaned at 60° against a chute; “table” test-sagging measured against ahorizontal plane; and Acermi test-sagging measured 35 cm from the edgeof a table).

Example: Particle Board Trial

Comparisons of the qualities of particle boards made using aurea-formaldehyde binder (UF E0) and using a carbohydrate polyamine(hexamethylenediamine) binder were carried out under the followingconditions.

-   -   Board size: 350×333 mm and mainly 10 mm thick (2×20 mm).    -   Platen temperature: 195° C. mainly but also, 175 and ˜215° C.    -   Pressure: 3.5 Mpa (35 bar) Quoted-Actual 35 Kg/cm², 56 bar to        achieve.    -   Density target: 650 kg/m³

Pre-form prepared prior to pressing.

Results:

PressTime IB Strength Binder (secs) (Mpa) UF E0 150 0.75 100 0.69 800.66 Carbohydrate 300 0.92 polyamine 240 0.99 180 0.88 150 0.73 120 0.6890 0.15All boards prepared appeared of high quality; no splits or degassingwere observed. The boards made with this carbohydrate polyamineformulation match urea formaldehyde board when they are cured for 150seconds.

The invention claimed is:
 1. A method of making a collection of matterbound with a cured, thermoset, polymeric binder, the method comprising:(i) providing a carbohydrate reactant, wherein the carbohydrate reactantcomprises a cellulose hydrolysate comprising one or more reducingsugars; (ii) providing 1,6-diaminohexane; (iii) preparing an uncuredaqueous binder solution containing reactants for producing the cured,thermoset, polymeric binder by combining the carbohydrate reactant andthe 1,6-diaminohexane; (iv) disposing the uncured aqueous bindersolution onto said collection of matter; and (v) thermally curing theuncured aqueous binder disposed on the collection of matter to form thecollection of matter bound with the cured, thermoset, polymeric binder.2. The method of claim 1, in which the cured, thermoset, polymericbinder is formaldehyde free.
 3. The method of claim 1, in which neitherformaldehyde nor phenol is used as a reagent.
 4. The method of claim 1,wherein the collection of matter comprises matter selected from thegroup consisting of glass fibers, mineral fibers, aramid fibers, ceramicfibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers,rayon fibers, cellulosic fibers, wood shavings, sawdust, wood pulp,ground wood, jute, flax, hemp, straw, particulates, coal particulatesand sand particulates.
 5. The method of claim 1, wherein the collectionof matter bound with the cured, thermoset, polymeric binder comprisesglass fibers present in the range from 70% to 99% by weight.
 6. Themethod of claim 1, wherein a weight ratio of the one or more reducingsugars of the cellulose hydrolysate to 1,6-diaminohexane is in the rangeof 2:1 to 10:1.
 7. The method of claim 1, wherein a weight ratio of theone or more reducing sugars of the cellulose hydrolysate to1,6-diaminohexane is in the range of 3:1 to 6:1.
 8. The method of claim1, wherein the collection of matter is a mineral fiber insulationproduct.
 9. The method of claim 1, wherein the one or more reducingsugars of the cellulose hydrolysate are selected from the groupconsisting of dextrose, xylose, fructose, and mixtures thereof.
 10. Themethod of claim 1, wherein the reactants for producing the cured,thermoset, polymeric binder further comprises one or more primarypolyamines H₂N-Q-NH₂, wherein Q is alkyl, cycloalkyl, heteroalkyl, orcycloheteroalkyl, each of which is optionally substituted.
 11. Themethod of claim 1, wherein the reactants consist essentially of the oneor more reducing sugars of the cellulose hydrolysate and1,6-diaminohexane.
 12. The method of claim 1, wherein the collection ofmatter and the cured, thermoset, polymeric binder further comprises amaterial selected from the group consisting of a silicon-containingcompound, gamma-aminopropyltriethoxysilane,gamma-glycidoxypropyltrimethoxysilane,aminoethylaminopropyltrimethoxysilane, an aminofunctional oligomericsilane, an aminofunctional oligomeric siloxane and mixtures thereof. 13.A method of making a composite wood board comprising a collection ofmatter comprising cellulosic fibers bound with a cured, thermoset,polymeric binder, the method comprising: (i) providing a carbohydratereactant, wherein the carbohydrate reactant comprises a cellulosehydrolysate comprising one or more reducing sugars; (ii) providing1,6-diaminohexane; (iii) preparing an uncured aqueous binder solutioncontaining reactants for producing the cured, thermoset, polymericbinder by combining the carbohydrate reactant and the 1,6-diaminohexane;(iv) disposing the uncured aqueous binder solution onto said collectionof matter comprising cellulosic fibers; and (v) thermally curing theuncured aqueous binder disposed on the collection of matter to form thecomposite wood board bound with the cured, thermoset, polymeric binder;wherein the composite wood board is selected from the group consistingof: a composite wood board having a modulus of elasticity (MOE) of atleast 1800 N/mm²; a composite wood board having a bending strength (MOR)of at least 18 N/mm²; a composite wood board having an internal bondstrength (TB) of at least 0.28 N/mm²; a composite wood board whichswells less than or equal to 12%, as measured by a change in thickness,after 24 hours in water at 20° C.; a composite wood board having a waterabsorption after 24 hours in water at 20° C. of less than or equal to40%; a composite wood board comprising a wax; an orientated strandboard;and a medium density fiberboard.
 14. The method of claim 13, wherein aweight ratio of the one or more reducing sugars of the cellulosehydrolysate to 1,6-diaminohexane is in the range of 2:1 to 10:1.
 15. Themethod of claim 13, wherein a weight ratio of the one or more reducingsugars of the cellulose hydrolysate to 1,6-diaminohexane is in the rangeof 3:1 to 6:1.
 16. The method of claim 13, wherein the one or morereducing sugars of the cellulose hydrolysate are selected from the groupconsisting of dextrose, xylose, fructose, and mixtures thereof.
 17. Themethod of claim 13, wherein the reactants for producing the cured,thermoset, polymeric binder further comprises one or more primarypolyamines H₂N-Q-NH₂, wherein Q is alkyl, cycloalkyl, heteroalkyl, orcycloheteroalkyl, each of which is optionally substituted.
 18. Themethod of claim 13, wherein the reactants consist essentially of the oneor more reducing sugars of the cellulose hydrolysate and1,6-diaminohexane.
 19. The method of claim 13, wherein the cellulosicfibers comprise matter selected from the group consisting of woodshavings, sawdust, wood pulp, ground wood, jute, flax, hemp and straw.20. The method of claim 13, wherein the composite wood board has from 8%to 18% by dry weight of the binder.
 21. A method of making a woodparticle board comprising a collection of matter comprising cellulosicfibers bound with a cured, thermoset, polymeric binder, the methodcomprising: (i) providing a carbohydrate reactant, wherein thecarbohydrate reactant comprises a cellulose hydrolysate comprising oneor more reducing sugars; (ii) providing 1,6-diaminohexane; (iii)preparing an uncured aqueous binder solution containing reactants forproducing the cured, thermoset, polymeric binder by combining thecarbohydrate reactant and the 1,6-diaminohexane; (iv) disposing theuncured aqueous binder solution onto said collection of mattercomprising cellulosic fibers; and (v) thermally curing the uncuredaqueous binder disposed on the collection of matter to form thecomposite wood board bound with the cured, thermoset, polymeric binder;wherein the wood particle board has the following features: a modulus ofelasticity (MOE) of at least 1800 N/mm², a bending strength (MOR) of atleast 18 N/mm², an internal bond strength (TB) of at least 0.28 N/mm²,it swells less than or equal to 12%, as measured by a change inthickness, after 24 hours in water at 20° C., and a water absorptionafter 24 hours in water at 20° C. of less than or equal to 40%.